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ON-LINE PUFF RESOLVED ANALYSIS OF CIGARETTE SMOKE FOR PRODUCT PROFILING USING SOFT-PHOTOIONISATION MASS SPECTROMETRY

Sven Ehlert1,2, Sören Iwe2, Jan Heide2, Matthias Bente v Frowein1, Andreas Walte1, Ralf Zimmermann2

Contact:

1 Photonion GmbH, 19061 Schwerin, Germany [www.photonion.de]

2 Universität Rostock, Institut für Chemie, Abt. Analytische Chemie & Massenspektrometrie-Zentrum,

18051 Rostock, Germany [www.uni-rostock.de]

Applications, Results & Discussion

PCA – Principle Component Analysis

Figure 2: Graphical

representation of a

principal component

analysis with original

coordinate system

[Kessler, Waltraud:

Multivariate Datenanalyse

für die Pharma-, Bio- und

Prozessanalytik. Wiley-

VCH, 2006]

Figure 4: Investigated cigarettes with (magenta) taped filter with

adhesive tape (black) holes in the cigarette paper, along the cigarette

(green) holes in the cigarette paper, in front of the filter the filter.

The PCA enable a fast overview and comparison option for multivariate data. To ensure good comparability between the cigarette brands examined, the raw data is

reduced by three times the blank before TIC standardization. If a negative signal occurs, it is set to zero. Generally the first component explains the includes the main

observed variation. By having a look into the loadings, the main influencing signals are nicotine (162 m/z) and isoprene (68 m/z). According to the first principal component,

only the non-filter and research cigarettes, as well as the Pall Mall Blue and Marlboro Gold brands can be identified as distinct groups. To archive a further grouping or

separation, the subordinate principal components need to be taken into account. In the figures they are shown up to the fourth principal component together with the

appearing clusters. In a second step of the study, the influence of defects in the cigarettes should be investigated. On the one hand to show the capabilities for quality

control purposes, but also to have a hint for counterfeit cigarettes, typically not having the same structure and tobacco as the original. The results can be seen in figure 4.

Introduction & Method

The cigarette market continues to enjoy high demand from

consumers. In doing so, the cigarette industry in Germany

generated a turnover of 21.6 billion euros in 2018 [1]. Such

high profits also attract the interest of the black market.

According to an estimate, 30% of all cigarette sales around

the world are counterfeited [2].

The worrying aspect of such a large number of counterfeits

and the very limited possibilities of identifying them is that

there is no control of the composition of tobacco and other

harmful additives for such cigarettes. The now strictly

regulated limits of nicotine, tar and carbon monoxide

content as well as already issued prohibitions of additives,

which are highly carcinogenic, do not apply to fake

cigarettes.

The cigarette brands on the German market and in large

parts of the world come from only a few manufacturers. For

example, the four largest tobacco companies in Germany

had a market share of approx. 87% in 2017.

This study is focusing on creating clearly identifiable profiles

of different cigarette brands. The differences between

smoke constituents and their ratio are investigated. Based

on this, the aim of this approach is to present a way in

which counterfeit or defective cigarettes can be

distinguished from the original ones by chemical analysis .

Mass spectra contain a great deal of information, which is available

in the form of thousands of data points. This wealth of information

can be explored using principal component analysis (PCA).

Figure 1: Experimental setup with the commercial available

LM2X Smoke Analyzer from Borgwaldt KC and Photonion

GmbH (Germany)

References

1. Deutscher Zigarettenverband (Hrsg.): Kennzahlen der Zigarettenindustrie. Unter den Linden 42, 10117 Berlin: Deutscher

Zigarettenverband, 2019

2. Fuchs, Hans J.: Piraten, Fälscher und Kopierer: Strategien und Instrumente zum Schutz geistigen Eigentums in der Volksrepublik

China. Springer-Verlag, 2006

3. Bundesministerium für Ernährung und Landwirtschaft (Hrsg.): Tabakzusatzstoffe. Bonn: Bundesministerium für Ernährung und

Landwirtschaft

Conclusion

The test setup consists of a two-channel smoke machine from

Borgwaldt KC, a deuterium lamp as ionization source for

photoionization by means of SPI (Single Photon Ionization) and a

reflectron-oaTOF mass spectrometer (orthogonal acceleration time

of flight). The ISO standard smoke protocol was used with the

following parameters: puff volume: 35 ml bell shape; puff duration 2

seconds; puff to puff delay: 60 seconds.

Table 1: Examined cigarette brands with associated manufacturer

and their nicotine, tar and carbon monoxide content per cigarette

[3]. * Reemtsma is a subsidiary of the tobacco company Imperial

Tobacco Group.

Even it is not easy to identify significant difference between the

cigarette brands, defects in the structure of the original cigarettes can

be detected very well by the principal component analysis. Thus, this

method could also be a way to identify counterfeit cigarettes.

Figure 3 a): PCA scores of cigarettes with filter (black) and without filter (red) b-d) PCA

scores and groupings of different filter cigarette brands and types by main component 1

vs. main components 2 to 4

a) b)

c) d)

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